CN101151319A - Oil-repellent composition and oil-repellent film - Google Patents
Oil-repellent composition and oil-repellent film Download PDFInfo
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- CN101151319A CN101151319A CNA2006800106851A CN200680010685A CN101151319A CN 101151319 A CN101151319 A CN 101151319A CN A2006800106851 A CNA2006800106851 A CN A2006800106851A CN 200680010685 A CN200680010685 A CN 200680010685A CN 101151319 A CN101151319 A CN 101151319A
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- oil repellent
- methyl
- acrylate
- oil
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Abstract
Disclosed is an oil-repellent composition containing a copolymer (A) and a solvent, wherein the copolymer (A) has a polymerization unit derived from a (meth)acrylate (a1) having a polyfluoroalkyl group, a polymerization unit derived from a (meth)acrylate (a2) having a blocked isocyanate group, and a polymerization unit derived from a (meth)acrylate (a3-1) having a hydroxyl group or a (meth)acrylic acid (a3-2). Also disclosed is an oil-repellent film obtained from such an oil-repellent composition. The oil-repellent composition enables to obtain an oil-repellent film which exhibits excellent and durable oil repellency and does not decrease in adhesion to a base material even when it is exposed to high-temperature oil for a long time. The oil-repellent film is excellent in oil repellency and durability.
Description
Technical field
The present invention relates to a kind of oil repellent composition and a kind of oil repellent film.
Background technology
As the oil sealing agent of the seepage of the fluid bearing position oil that is used for preventing motors such as electronics, used the oil repellent reagent that comprises fluoropolymer.For example, fluid bearing position at the cooling fan motor that is used for microprocessor, CD rotating equipment, hard disc of computer etc., the end surface of bearing or axle sleeve is provided with the oil repellent film that comprises oil repellent reagent, this oil repellent reagent comprises fluoropolymer, with the seepage (for example referring to patent document 1) of the oil that prevents to fill as lubricant in bearing.In addition, as the fluorinated copolymer with oil repellent, known have a polymkeric substance (for example referring to patent document 2) with fluorine-containing aliphatics ring texture.
Yet because the heat that motor partly produces, the temperature of the oil of fluid bearing part can raise, and this oil repellent film is exposed in the high temperature oil, makes permeable sometimes this oil repellent film of oil.Therefore, the oil repellent film can expand, or this oil repellent film can reduce the tack of bearing or axle sleeve, therefore reduces the oil repellent of oil repellent film, produces the problem that the function that prevents oil seepage is weakened.
As the fluorine resin composition that base material is had excellent adhesion, proposed a kind of composition, it comprises fluorine resin with fluorine-containing ring texture and the fluorochemicals (referring to patent document 3) that has polar functional group and dissolve in fluorine-based solvent.Yet this fluorine resin with fluorine-containing ring texture has ehter bond in its ring texture, makes that it is unbodied.Therefore, it can not demonstrate surface polarity, so its oil repellent is insufficient, causes existing the risk that can not refuse oil.
In addition, as oil repellent reagent, known a kind of composition that comprises polymkeric substance, described polymkeric substance have the polymerized unit (for example referring to patent document 4) of (methyl) acrylate that is derived from polyfluorinated alkyl.
Yet said composition has good initial oil repellent as the oil sealing agent, but it has the relatively poor problem of oil repellent characteristic.
In addition, common oil sealing agent is limpid colourless, and the visual confirmation of its film is very difficult, therefore can not assess the coating state of oil sealing agent, can cause the problem that is difficult to guarantee stabilised quality like this.At this problem, proposed a kind of coloured material that can evaporate that will be characterised in that and mixed 90 ℃～150 ℃ following heating, and the technology of before heating, checking (referring to patent document 5).
Yet, in the situation of patent document 5 because the evaporation after the heating has reduced painted degree, cause can not visual confirmation oil repellent film the coating state.Under the situation that in heat-processed, comes off or peel off, be difficult to the final state of assessment oil repellent film.In addition, when the parts that do not apply with the oil sealing agent are blended in wherein, can produce the problem that to select.
Patent document 1:JP-A-2000-297818
Patent document 2:JP-A-63-238111
Patent document 3:JP-A-2004-115622
Patent document 4:JP-A-2000-160148
Patent document 5:JP-A-2004-211851
Summary of the invention
The technical problem that solves
One object of the present invention be to provide a kind of can access have good oil repellent in addition when being exposed in the high temperature oil for a long time its tack to base material yet can not reduce and have the oil repellent composition of the good oil repellent film of refusing oily weather resistance, and provide a kind of oil repellent film that has good oil repellent and refuse oily weather resistance.
In addition, another object of the present invention is to provide a kind of oil repellent composition that can access oil repellent film, and a kind of oil repellent film with good visual confirmation is provided with good visual confirmation.
The technique means of dealing with problems
Oil repellent composition of the present invention is characterised in that it comprises: multipolymer (A), its have (methyl) acrylate (a1) that is derived from polyfluorinated alkyl polymerized unit, be derived from the polymerized unit of (methyl) acrylate (a2) that contains the blocked isocyanate base and be derived from (methyl) acrylate (a3-1) of hydroxyl or the polymerized unit of (methyl) vinylformic acid (a3-2); And solvent.
Above-mentioned multipolymer (A) can also have the polymerized unit that is derived from (methyl) acrylate (a4) that contains alkyl.
The ratio of polymerized unit in above-mentioned multipolymer (A) that is derived from (methyl) acrylate (a1) is 70～98 quality % of total polymerization unit (100 quality %).
Preferred above-mentioned oil repellent composition also comprises at least a coloured material.
Above-mentioned coloured material is preferably the fluorescent color material.
Oil repellent film of the present invention is characterised in that it comprises multipolymer (A), this multipolymer (A) have (methyl) acrylate (a1) that is derived from polyfluorinated alkyl polymerized unit, be derived from the polymerized unit of (methyl) acrylate (a2) that contains the blocked isocyanate base and be derived from (methyl) acrylate (a3-1) of hydroxyl or the polymerized unit of (methyl) vinylformic acid (a3-2).
Above-mentioned multipolymer (A) can also have the polymerized unit that is derived from (methyl) acrylate (a4) that contains alkyl.
The ratio of polymerized unit in above-mentioned multipolymer (A) that is derived from (methyl) acrylate (a1) is preferably 70～98 quality % of total polymerization unit (100 quality %).
Preferred above-mentioned oil repellent composition also comprises at least a coloured material.
Above-mentioned coloured material is preferably the fluorescent color material.
Beneficial effect
According to oil repellent composition of the present invention, can obtain having good oil repellent in addition when being exposed in the high temperature oil for a long time its tack to base material yet can not reduce and have the good oil repellent film of refusing oily weather resistance.
Oil repellent film of the present invention has good oil repellent and refuses oily weather resistance, and good visual confirmation.
Embodiment
(multipolymer (A))
Multipolymer (A) comprise (methyl) acrylate (a1 hereinafter referred to as) that is derived from polyfluorinated alkyl polymerized unit, be derived from the polymerized unit of (methyl) acrylate (a2 hereinafter referred to as) that contains the blocked isocyanate base and be derived from (methyl) acrylate (a3-1 hereinafter referred to as) of hydroxyl or the polymerized unit of (methyl) vinylformic acid (a3-2 hereinafter referred to as).Term among the present invention " (methyl) acrylate " is meant acrylate or methacrylic ester, and term " (methyl) vinylformic acid " is meant acrylic or methacrylic acid.
For a1, be preferably by the compound shown in the following formula [1], wherein R
fThe expression Polyfluoroalkyl, Q represents divalent organic group, R represents hydrogen atom or methyl.
[formula 1]
R
fBe preferably the alkyl that wherein two or more hydrogen atoms are replaced by fluorine atom.R
fIn carbonatoms be preferably 2～20, more preferably 4～16.R
fCan have linear chain structure or branched structure, be preferably linear chain structure.Under the situation of branched structure, preferably prop up chain portion and be positioned at R
fThe end, and it is the short chain with 1～4 carbon atom.R
fCan contain the Sauerstoffatom of ether or the sulphur atom of thioether.R
fEnd construction comprise CF
3CF
2-, (CF
3)
2CF-, CF
2H-, CFH
2-etc., be preferably CF
3CF
2-.
When using [(R
fIn number of fluorine atoms)/(with R
fHave the number of hydrogen atoms that comprises in the alkyl of equal amts carbon atom)] * 100 expression R
fDuring the quantity of fluorine atom, it is preferably 60% or bigger, more preferably 80% or bigger, most preferably be 100%.Under 100% situation, R
fBe also referred to as perfluoroalkyl and (hereinafter be also referred to as R
FBase).
R
FCarbonatoms in the base is preferably 2～20, and more preferably 4～16.Work as R
FCarbonatoms in the base is in this scope the time, and the polymerizability of a1 and the stability of solution after polymerization are fine, and this oil repellent composition has good initial oil repellent and refuses oily weather resistance.
R
fSpecific examples comprise following group (comprising the structural isomerism group) etc.:
C
4F
9-: F (CF
2)
4-, (CF
3)
2CFCF
2-, (CF
3)
3C-, CF
3CF
2(CF
3) CF-etc.;
C
5F
11-: F (CF
2)
5-etc.;
C
6F
13-: F (CF
2)
6-etc.;
C
7F
15-: F (CF
2)
7-, (CF
3)
2CF (CF
2)
4-etc.;
C
8F
17-: F (CF
2)
8-etc.;
C
9F
19-: F (CF
2)
9-, (CF
3)
2CF (CF
2)
6-etc.;
C
10F
21-: F (CF
2)
10-etc.;
C
12F
25-: F (CF
2)
12-etc.;
C
13F
27-: (CF
3)
2CF (CF
2)
8-etc.;
C
14F
29-: F (CF
2)
14-etc.; With
C
16F
33-: F (CF
2)
16-etc.
At R
fHave under the situation of sulphur atom of the Sauerstoffatom of ether or thioether, its specific examples comprises following group, and wherein k represents 1～5 integer:
F(CF
2)
kOCF(CF
3)-；
F(CF
2CF
2O)
kCF
2CF
2-；
F(CF
2CF
2CF
2O)
kCF
2CF
2-；
F[CF(CF
3)CF
2O]
kCF(CF
3)-；
F[CF(CF
3)CF
2O]
kCF(CF
3)CF
2CF
2-；
F(CF
2)
kSCF(CF
3)-；
F(CF
2CF
2S)
kCF
2CF
2-；
F(CF
2CF
2CF
2S)
kCF
2CF
2-；
F[CF(CF
3)CF
2S]
kCF
2CF
2-；
F[CF (CF
3) CF
2S]
kCF (CF
3) CF
2CF
2-; Deng.
For R
f, straight chain R more preferably
FBase.Particularly, F (CF
2)
4-, F (CF
2)
5-, F (CF
2)
6-, F (CF
2)
7-, F (CF
2)
8-, F (CF
2)
9-, F (CF
2)
10-, F (CF
2)
11-and F (CF
2)
12-be particularly preferred.
Q comprises following group, wherein R
aExpression hydrogen atom or alkyl, p and q represent 0 or 1 or bigger integer separately respectively, and p+q is 1～22 integer:
-(CH
2)
p+q-；
-(CH
2)
pCONR
a(CH
2)
q-；
-(CH
2)
pOCONR
a(CH
2)
q-；
-(CH
2)
pSO
2NR
a(CH
2)
q-；
-(CH
2)
pNHCONH(CH
2)
q-；
-(CH
2)
pCH(OH)(CH
2)
q-；
-(CH
2)
pCH (OCOR
a) (CH
2)
q-; Deng.
For Q, more preferably-(CH
2)
P+q-,-(CH
2)
pCONR
a(CH
2)
q-or-(CH
2)
pSO
2NR
a(CH
2)
q-(p represents 0 or 1 or bigger integer, and q represents 2 or bigger integer, and P+q is 2～6), most preferably ethylidene, propylidene, butylidene, pentylidene or hexylidene.
For a1, preferably following compound, wherein R represents hydrogen atom or methyl:
F(CF
2)
4CH
2OCOCR＝CH
2[1-1]；
F(CF
2)
5CH
2OCOCR＝CH
2[1-2]；
H(CF
2)
4CH
2OCOCR＝CH
2[1-3]；
H(CF
2)
6CH
2OCOCR＝CH
2[1-4]；
H(CF
2)
8CH
2OCOCR＝CH
2[1-5]；
H(CF
2)
10CH
2OCOCR＝CH
2[1-6]；
H(CF
2)
8CH
2CH
2OCOCR＝CH
2[1-7]；
F(CF
2)
4CH
2CH
2OCOCR＝CH
2[1-8]；
F(CF
2)
6CH
2CH
2OCOCR＝CH
2[1-9]；
F(CF
2)
8CH
2CH
2OCOCR＝CH
2[1-10]；
F(CF
2)
9CH
2CH
2OCOCR＝CH
2[1-11]；
F(CF
2)
10CH
2CH
2OCOCR＝CH
2[1-12]；
F(CF
2)
12CH
2CH
2OCOCR＝CH
2[1-13]；
F(CF
2)
14CH
2CH
2OCOCR＝CH
2[1-14]；
F(CF
2)
16CH
2CH
2OCOCR＝CH
2[1-15]；
F(CF
2)
8(CH
2)
3OCOCR＝CH
2[1-16]；
F(CF
2)
8(CH
2)
4OCOCR＝CH
2[1-17]；
(CF
3)
2CF(CF
2)
4CH
2CH
2OCOCR＝CH
2[1-18]；
(CF
3)
2CF(CF
2)
6CH
2CH
2OCOCR＝CH
2[1-19]；
(CF
3)
2CF(CF
2)
8CH
2CH
2OCOCR＝CH
2[1-20]；
(CF
3)
2CF(CF
2)
5(CH
2)
3OCOCR＝CH
2[1-21]；
(CF
3)
2CF(CF
2)
5CH
2CH(OH)CH
2OCOCR＝CH
2[1-22]；
(CF
3)
2CF(CF
2)
7CH
2CH(OH)CH
2OCOCR＝CH
2[1-23]；
(CF
3)
2CF(CF
2)
5CH
2CH(OCOCH
3)OCOCR＝CH
2[1-24]；
F(CF
2)
8SO
2N(CH
3)CH
2CH
2OCOCR＝CH
2[1-25]；
F(CF
2)
8SO
2N(C
2H
5)CH
2CH
2OCOCR＝CH
2[1-26]；
F (CF
2)
8SO
2N (C
3H
7) CH
2CH
2OCOCR=CH
2[1-27]; With
F(CF
2)
8CONHCH
2CH
2OCOCR＝CH
2[1-28]。
For a1, in [1-1]～[1-28], [1-3]～[1-15] is preferred, and [1-8]～[1-13] is most preferred.
A2 is by containing the compound that isocyanate group (methyl) acrylate and block agent reaction obtains.
(methyl) acrylate that contains isocyanate group comprises 2-isocyanatoethyl (methyl) acrylate, 1,3,3-trimethylammonium-4-isocyanato-cyclohexyl methyl amino oxygen ethyl (methyl) acrylate etc.
The block agent comprises 2-butanone oxime, cyclohexanone-oxime, ε-Ji Neixianan, methyl aceto acetate, methyl ethyl diketone, phenol, methyl alcohol, diethyl malonate, hydrosulphite, pyrazoles, 3-methylpyrazole, 3, indazole etc.In these block agent, more preferably 2-butanone oxime, diethyl malonate, pyrazoles, 3-methylpyrazole and 3.Most preferably 2-butanone oxime, 3-methylpyrazole and 3 are because they have advantages of excellent stability and good reactivity.
A3-1 comprises (methyl) vinylformic acid 2-hydroxyl ethyl ester, (methyl) vinylformic acid 2-hydroxypropyl acrylate, (methyl) vinylformic acid 4-hydroxy butyl ester, 1,4 cyclohexane dimethanol list (methyl) acrylate, 2-acryloxy ethyl-2-hydroxyethyl phthalic acid, (methyl) vinylformic acid 3-chloro-2-hydroxypropyl acrylate, polyoxyalkylene list (methyl) acrylate, polyoxyethylene list (methyl) acrylate, polyoxypropylene list (methyl) acrylate, single (methyl) acrylate of polyoxyethylene/polyoxypropylene etc.
By using a2 and a3-1 or a3-2 (a3-1 and a3-2 hereinafter also are called a3 jointly), (methyl) acrylate of (methyl) acrylate of a1 and a2 or a3 increases the molecular weight of multipolymer (A) through copolymerization.In addition, when forming the oil repellent film, carboxylic acid group's interreaction of (methyl) acrylate of a2 and the hydroxyl of a3-1 or a3-2 forms amino-formate bond, forms three-dimensional cross-linked product thus.The oil repellent film that uses this high molecular weight copolymer (A) and form three-dimensional cross-linked product shows the good oily weather resistance of refusing, even also can not expand or peel off in immersing high temperature oil the time.
Multipolymer (A) can further have the polymerized unit that is derived from (methyl) acrylate (hereinafter being called a4) that contains alkyl.R in a1
FThe carbonatoms of base preferably had the polymerized unit that is derived from a4 greater than 8 o'clock.
A4 comprises (methyl) methyl acrylate, (methyl) ethyl propenoate, (methyl) propyl acrylate, (methyl) butyl acrylate, (methyl) cyclohexyl acrylate, (methyl) 2-EHA, the just own ester of (methyl) vinylformic acid, (methyl) vinylformic acid 3-ethoxy ethyl ester, (methyl) vinylformic acid 3-benzoyl ester, (methyl) isobutyl acrylate, (methyl) tert-butyl acrylate, (methyl) decyl acrylate, (methyl) vinylformic acid dodecane ester, (methyl) vinylformic acid octadecane ester, (methyl) isobornyl acrylate (isoburnyl (meth) acrylate), the positive lauryl of (methyl) vinylformic acid, (methyl) vinylformic acid tridecane ester, (methyl) tetrahydrofurfuryl acrylate, (methyl) vinylformic acid benzene methyl, (methyl) vinylformic acid phenoxy ethyl, (methyl) isobornyl acrylate etc.In (methyl) acrylate of these a4, (methyl) ethyl propenoate, (methyl) propyl acrylate and (methyl) cyclohexyl acrylate are preferred.
By using molecular weight is 200 or lower a4, and (methyl) acrylate that makes (methyl) acrylate of a1 and a4 is through copolymerization, thereby the molecular weight of multipolymer (A) is increased.In addition, the alkyl that is derived from the polymerized unit of a4 can suppress based on the R in the polymerized unit of a1
FThe crystallinity of base, thus multipolymer (A) separating out in the oil repellent composition suppressed.Therefore, this oil repellent composition becomes homogeneous phase solution, and its stability in storage is improved.In addition, by comprising the polymerized unit that is derived from a4, the film-forming properties of this oil repellent composition is improved, and can obtain uniform film.Further, molecular weight be 200 or the use of lower a4 improved the crystallinity of oil repellent film, improved dynamic wettability, for example receding contact angle can easily roll (rolling) oil, can make oily mandatory inclosure.
Multipolymer (A) can have the polymerized unit that is derived from the polymerisable monomer (hereinafter being called a5) that is different from a1, a2, a3 and a4.When it had the polymerized unit that is derived from a5, it had the excellent adhesion to base material.A5 comprises glycidyl (methyl) acrylate, aziridinyl (methyl) acrylate, (methyl) acrylate that comprises the polydimethylsiloxane base, triallyl cyanurate, dialkyl maleate, (methyl) vinylformic acid N-substituted-amino alkyl ester, (methyl) vinylformic acid polyoxyalkylene glycol ester etc.
In multipolymer (A), be derived from the polymerized unit of a1, the polymerized unit that is derived from a2, the polymerized unit that is derived from the polymerized unit of a3 and is derived from a4 respectively can single use or its two or more use together.When comprising two or more polymerized units that are derived from a1, the R of each a1
fCarbonatoms preferably differ from one another.In addition, be derived from R in the polymerized unit of a1 when two or more
fCarbonatoms not simultaneously, the R of a1
fCarbonatoms be expressed as its mean value.
The polymerized unit shared ratio in multipolymer (A) that is derived from a1 is preferably 70～98 quality % of total polymerization unit (100 quality %), and more preferably 80～98 quality % most preferably are 85～98 quality %.When the polymerized unit that is derived from a1 was in this scope, this oil repellent film had good oil repellent.
The polymerized unit shared ratio in multipolymer (A) that is derived from a2 is preferably 0.5～10 quality % of total polymerization unit (100 quality %), and more preferably 1～8 quality % most preferably is 1～5 quality %.
The polymerized unit shared ratio in multipolymer (A) that is derived from a3 is preferably 0.5～10 quality % of total polymerization unit (100 quality %), and more preferably 1～8 quality % most preferably is 1～5 quality %.
When the polymerized unit that is derived from a2 and the polymerized unit that is derived from a3 are in this scope, then fully form three-dimensional cross-linked product, keep the oil repellent of final oil repellent film simultaneously, and show sufficient tack, cause the good oily weather resistance of refusing.
The polymerized unit shared ratio in multipolymer (A) that is derived from a4 is preferably 20 quality % or littler.Yet, R in a1
fThe carbonatoms of base was greater than 8 o'clock, and the polymerized unit shared ratio in multipolymer (A) that is derived from a4 is preferably 0.5～20 quality % of total polymerization unit (100 quality %), and more preferably 1～20 quality % most preferably is 1.5～15 quality %.As a4 during in this scope, this oil repellent composition has good stability in storage and film-forming properties.
(solvent)
Solvent comprises halogen compounds, hydro carbons, ketone, ester class, ethers, nitrogen compound, sulphur compound, inorganic solvent, organic acid etc.
Halogen compounds comprises halohydrocarbon, halogen ether etc.
Halohydrocarbon comprises HCFC, fluorocarbon, hydrogen bromine carbon compound, fluorine-containing alcohol etc.
HCFC comprises following compound:
CH
3CCl
2F；
CHCl
2CF
2CF
3；
CHClFCF
2CClF
2Deng.
Fluorocarbon comprises following compound:
CF
3CF
2CF
2CHF
2；
CF
3CF
2CF
2CH
2F；
CF
3CF
2CH
2CF
3；
CHF
2CF
2CF
2CHF
2；
CHF
2CH
2CF
2CF
3；
CF
3CHFCH
2CF
3；
CF
3CH
2CF
2CHF
2；
CHF
2CHFCF
2CHF
2；
CF
3CHFCF
2CH
3；
CHF
2CHFCHFCHF
2；
CF
3CH
2CF
2CH
3；
CF
3CF
2CH
2CH
3；
CHF
2CH
2CF
2CH
3；
CHF
2CF
2CF
2CF
2CF
3；
CF
3CF
2CF
2CHFCF
3；
CHF
2CF
2CF
2CF
2CHF
2；
CF
3CHFCHFCF
2CF
3；
CF
3CHFCF
2CH
2CF
3；
CF
3CF(CF
3)CH
2CHF
2；
CF
3CH(CF
3)CH
2CF
3；
CF
3CH
2CF
2CH
2CF
3；
CHF
2CHFCF
2CHFCHF
2；
CHF
2CF
2CF
2CHFCH
3；
CF
3CH
2CH
2CH
2CF
3；
CHF
2CH
2CF
2CH
2CHF
2；
CF
3(CF
2)
4CHF
2；
CF
3(CF
2)
4CH
2F；
CF
3CF
2CF
2CF
2CH
2CF
3；
CHF
2CF
2CF
2CF
2CF
2CHF
2；
CF
3CH(CF
3)CHFCF
2CF
3；
CF
3CF
2CH
2CH(CF
3)CF
3；
CF
3CH
2CF
2CF
2CH
2CF
3；
CF
3CF
2CH
2CH
2CF
2CF
3；
CF
3CF
2CF
2CF
2CH
2CH
3；
CF
3CH(CF
3)CH
2CH
2CF
3；
CHF
2CF
2CH
2CH
2CF
2CHF
2；
CF
3CF
2CF
2CH
2CH
2CH
3Deng.
Fluorine-containing alcohol comprises trifluoroethanol, 2,2,3,3,3-five fluoro-1-propyl alcohol, 2-(five fluorine butyl) ethanol, 2-(perfluor exysil) ethanol, 2-(perfluoro hexyl) ethanol, 2-(perfluor decyl) ethanol, 2-(perfluor-3-methyl butyl) ethanol, 1H, 1H, 3H-tetrafluoro-1-propyl alcohol, 1H, 1H, 5H-octafluoro-1-enanthol, 1H, 1H, 9H-ten hexafluoros-1 nonyl alcohol, 2H-hexafluoro-2-2-propyl alcohol, 1H, 1H, 3H-hexafluoro-2-butanols etc.
Hydrogen bromine carbon compound comprises following compound:
CH
2Br
2；
CH
2BrCH
2CH
3；
CH
3CHBrCH
3；
CH
2BrCHBrCH
3Deng.
Halogen ether comprises hydrogen fluorine ether.
Hydrogen fluorine ether comprises divergence type hydrogen fluorine ether and non-divergence type hydrogen fluorine ether.Divergence type hydrogen fluorine ether is a kind of wherein perfluoroalkyl or perfluorinated alkylidene and alkyl or the alkylidene group Sauerstoffatom compound connected to one another by ether.Non-divergence type hydrogen fluorine ether is a kind of hydrogen fluorine ether that comprises partially fluorinated alkyl or alkylidene group.
Divergence type hydrogen fluorine ether comprises following compound:
CF
3CF
2CF
2OCH
3；
(CF
3)
2CFOCH
3；
CF
3CF
2CF
2OCH
2CH
3；
CF
3CF
2CF
2CF
2OCH
3；
(CF
3)
2CFCF
2OCH
3；
(CF
3)
3COCH
3；
CF
3CF
2CF
2CF
2OCH
2CH
3；
(CF
3)CFCF
2OCH
2CH
3；
(CF
3)
3COCH
2CH
3；
CF
3CF(OCH
3)CF(CF
3)
2；
CF
3CF(OCH
2CH
3)CF(CF
3)
2；
C
5F
11OCH
2CH
3；
CF
3CF
2CF
2CF(OCH
2CH
3)CF(CF
3)
2；
CH
3O(CF
2)
4OCH
3；
CH
3OCF
2CF
2OCH
2CH
3；
C
3H
7OCF(CF
3)CF
2OCH
3；
F (CF
2)
nOCH
3(n is 6～10); Deng.
Non-divergence type hydrogen fluorine ether comprises following compound:
CHF
2OCF
2OCHF
2；
CH
2FCF
2OCHF
2；
CF
3CF
2CF
2OCH
2F；
CF
3CF
2OCH
2CHF
2；
CHF
2CF
2OCH
2CF
3；
CHF
2CF
2CH
2OCF
3；
CF
3CF
2CH
2OCHF
2；
CHF
2CF
2OCH
2CHF
2；
CF
3CH
2OCF
2CH
2F；
CF
3CH
2OCF
2CHF
2；
CHF
2CF
2CF
2OCH
3；
CHF
2CF
2CH
2OCH
3；
CF
3CF
2CF
2OCH
2CF
3；
CF
3CF
2CH
2OCF
2CF
3；
CF
3CF
2CF
2OCH
2CHF
2；
CF
3CF
2CH
2OCF
2CHF
2；
CHF
2CF
2CH
2OCF
2CF
3；
CHF
2CF
2CH
2OCF
2CHF
2；
CF
3CHFCF
2CH
2OCF
3；
CF
3CHFCF
2CH
2OCHF
2；
CF
3CF
2CF
2CH
2OCH
3；
(CF
3)
2CHCF
2OCH
3；
CF
3CF
2CF
2OCH
2CF
2CF
3；
CF
3CF
2CF
2OCH
2CF
2CHF
2；
CF
3CF
2CF
2CF
2OCF
2CHF
2；
CF
3(CF
2)
5OCHF
2；
CHF
2OCF
2CF
2OCHF
2；
CHF
2OCF
2OCF
2CF
2OCHF
2；
CHF
2OCF
2OCF
2OCF
2OCHF
2Deng.
Hydro carbons comprises aliphatic hydrocarbon, alicyclic hydrocarbon, aromatic hydrocarbon etc.
Aliphatic hydrocarbon comprises pentane, 2-methylbutane, 3-methylpentane, hexane, 2,2-dimethylbutane, 2,3-dimethylbutane, heptane, octane, pure isooctane, 2,2,3-trimethyl cyclohexane, decane, undecane, dodecane, 2,2,4,6,6-five methylheptane, tridecane, the tetradecane, n-Hexadecane etc.
Alicyclic hydrocarbon comprises pentamethylene, methylcyclopentane, hexanaphthene, methylcyclohexane, ethylcyclohexane etc.
Aromatic hydrocarbon comprises benzene,toluene,xylene etc.
Ketone comprises acetone, methyl ethyl ketone, 2 pentanone, methyl-n-butyl ketone, methyl iso-butyl ketone (MIBK) etc.
The ester class comprises methyl acetate, ethyl acetate, butylacetate, methyl propionate, methyl lactate, ethyl lactate, amyl lactate etc.
Ethers comprises diisopropyl ether, two alkane, tetrahydrofuran (THF) etc.
Nitrogen compound comprises pyridine, N, dinethylformamide, N,N-dimethylacetamide, N-methyl-pyrrolidone etc.
Sulphur compound comprises methyl-sulphoxide, tetramethylene sulfone etc.
Inorganic solvent comprises liquid carbon dioxide etc.
Organic acid comprises acetate, propionic acid, oxysuccinic acid, lactic acid etc.
As solvent, preferably HCFC, fluorocarbon, hydrogen fluorine ether and perfluoro-carbon, with regard to solvability, CH more preferably
3CCl
2F, CHCl
2CF
2CF
3, CHClFCF
2CClF
2, CH
2FCF
2OCHF
2, CF
3CF
2CF
2OCH
2F, CF
3CF
2OCH
2CHF
2, CHF
2CF
2OCH
2CF
3, CHF
2CF
2CH
2OCF
3, CF
3CF
2CH
2OCHF
2, CHF
2CF
2OCH
2CHF
2, CF
3CH
2OCF
2CH
2F, CF
3CH
2OCF
2CHF
2, CHF
2CF
2CF
2OCH
3, CF
3(CF
2)
4CHF
2, CF
3(CF
2)
4CH
2F and CF
3(CF
2)
5OCH
3These solvents have good solvability to polymkeric substance, and have good stability in storage under solution state.
Solvent can be separately or is used as its two or more mixture.
(oil repellent composition)
Oil repellent composition of the present invention is a kind of composition that comprises polymkeric substance (A) and solvent.
The content of polymkeric substance (A) in the oil repellent composition is preferably 0.1～20 quality % of oil repellent composition (100 quality %), more preferably 0.1～10 quality %.When its content was in this scope, this oil repellent composition had good oil repellent and refuses oily weather resistance.
The content of solvent in the oil repellent composition is preferably 80～99.9 quality % of oil repellent composition (100 quality %), more preferably 90～99.9 quality %.When its content was in this scope, this oil repellent composition had the good oily weather resistance of refusing, and this oil repellent film can form by primary coating.
In order to improve the tack of this oil repellent film, can be in oil repellent composition of the present invention add silane coupling agent, priming paint etc. with the degree of the storage stability of the oil repellent that can not influence the oil repellent film and oil repellent composition to base material.
For the oil repellent that improves the oil repellent film with refuse oily weather resistance, can in oil repellent composition of the present invention, add the fluoropolymer of the polymerization single polymerization monomer that does not contain (methyl) acrylate that is derived from polyfluorinated alkyl.This fluoropolymer comprises the polymkeric substance that has fluorine-containing aliphatics ring texture on its main chain described in JP-A-63-238111, PFPE, tetrafluoraoethylene-hexafluoropropylene copolymer, tetrafluoroethylene-perfluoroalkyl vinyl ether copolymer etc.
(coloured material)
Preferably in oil repellent composition of the present invention, add coloured material, for example dyestuff or pigment.When being mixed with coloured material, whether the existence of oil repellent film becomes is seen easily, causes it to have good visibility.
When adding coloured material, it can directly add in the oil repellent composition, perhaps when it is insoluble to the oil repellent composition, can with this coloured material with can the solvent phase compatible with coloured material mix with this oil repellent composition after interpolation again.
Coloured material preferably can show with the base material distinct colors and have high absorbance, more preferably even when base material is black, still can be luminous during with UV-irradiation, therefore can make the oil repellent film be able to the fluorescent color material of visual confirmation.When the light with the fluorescence maximum wavelength with this coloured material shone, this fluorescent color material provided stronger light emission, and it can make the oil repellent film be able to visual confirmation easily.Preferably even the coloured material that after with the heating of this oil repellent composition, still can recognize, the coloured material that its color still keeps easily more preferably even under the heat curing temperature of this oil repellent composition, the coloured material that its color still keeps easily during heating most preferably even under 80 ℃ or higher temperature.
This coloured material comprises tonka bean camphor, Stilbene, thiophene, xanthene, naphthaloid, pyrazoline, azoles, naphthalimide, indigo, acridine etc.With regard to thermotolerance, Stilbene, xanthene and naphthaloid are preferred.Two or more coloured materials can mix.
The addition of coloured material is preferably 0.1～30 quality % in the oil repellent film (100 quality %), more preferably 1～10 quality %.When it is 0.1 quality % or when bigger, this oil repellent film is very good aspect colour developing, and this oil repellent film can be by visual confirmation.In addition, 30 quality % or cause coloured material can not separate out more for a short time, separation that can genetic horizon from this oil repellent film.
(oil repellent film)
Oil repellent film of the present invention is the film that comprises above-mentioned multipolymer (A).
Oil repellent film of the present invention is by for example oil repellent composition of the present invention being coated on the base material, solvent being evaporated fully form.Coating method comprises spraying, dipping, brushing, pouring, spin coating etc.
Base material comprises resin, metal, fiber etc.Can carry out pre-treatment, prime treatment etc. to base material, for example corona treatment or ultraviolet and ozone are handled.This processing has improved the tack of oil repellent film to base material.
Oil repellent film of the present invention is a kind of film that is cross-linked to form by the oil repellent composition, crosslinked its tack to base material of having improved.Be used for crosslinked this oil repellent method for compositions comprise be heating and curing, the photocuring by ultraviolet radiation, the electrocuring by electromagenetic wave radiation or electron beam irradiation etc.Wherein, preferably be heating and curing, it only needs more a spot of fund input, and can not produce deleterious light beam.Preferably, for the curing that promotes functional group, combine with the Chemical bond and the grappling of base material, the temperature that is heating and curing is higher, the temperature that preferred heating can tolerate up to base material.Heating temperature is preferably 100～200 ℃, more preferably 100～150 ℃.Be preferably 30 minutes or longer heat-up time.In the time of in this temperature range and this time range, this oil repellent film is solidified well, obtains to have the oil repellent film of good oil repellent.
In oil repellent film of the present invention, can recognize isocyanate group and hydroxyl or carboxylic acid group's reaction in the multipolymer (A), to improve the molecular weight of multipolymer (A).In addition, can recognize that this oil repellent film has reduced the solvability of oil owing to the existence of the amino-formate bond (crosslinking structure) between isocyanate group and hydroxyl or the carboxylic acid group.Further, owing to there is a large amount of R
fBase, the oil repellent film has good oil repellent, makes even exposure is during the long period in the oil at 100 ℃ or higher temperature, and it can not decompose or dissolve yet, it has good tack to base material, can keep the long term and can not weaken its initial oil repellent to a great extent.
Embodiment
(embodiment: example 1～7, Comparative Examples: example 8～10) present invention is described, but the present invention should not be interpreted as being defined in this with reference to specific examples below.
Carry out the oil repellent evaluation according to following method.
(initial oil repellent)
The n-hexadecane of about 1 μ L is dripped on the test panel, measure its contact angle.Judge its oil sealing with the contact angle of n-hexadecane.The above contact angle of 50 degree is judged as has oil sealing, and being judged as less than 50 contact angles of spending does not have oil sealing.
(refusing oily weather resistance)
Test panel was flooded 40 hours in 120 ℃ n-hexadecane, take out, use the air cannon drying then.Then, measure the contact angle of n-hexadecane in the same manner as described above.
(contact angle)
Use CA-A, Kyowa Interface Science Co., Ltd. carries out the measurement of contact angle by sessile drop method under 25 ℃ condition.
[example 1]
In the glass flask of 50mL, add 5.7g vinylformic acid perfluoro hexyl ethyl ester [F (CF
2)
6CH
2CH
2OCOCH=CH
2] (C6FA hereinafter referred to as), 0.12g wherein methacrylic acid 2-isocyanato ethyl ester (IS hereinafter referred to as), the 0.09g1 of isocyanate group and 3 block, 4-cyclohexanedimethanol monomethacrylates [CH
2=CH (CH
3) COOCH
2C
6H
10CH
2OH] (hereinafter being called CM), 0.09g 2,2 '-azo two [2-methylbutyronitrile] (hereinafter being called AB1) and 13.5g HCF
2CF
2OCH
2CF
3(hereinafter being called solvent Y).
With the gas of nitrogen replacement flask interior, sealing then.Flask was kept 15 hours in 60 ℃ hot water bath, stir its inside simultaneously, obtain comprising the clear solution of multipolymer.Use 1 micron filter paper to separate by the solution that filters solid impurity and formation, with the filtrate dilution of solvent Y to forming, the preparation polymer concentration is the oil repellent solution of 2 quality %.
The oil repellent solution that forms was being applied 20 seconds on the SUS plate through cleaning under the condition of 500rpm by spin-coating method, and, obtaining having the test panel of oil repellent film 120 ℃ of thermal treatments 60 minutes.To this test panel, estimate its initial oil repellent and refuse oily weather resistance.It the results are shown in table 1.
[example 2]
Obtain test panel in the mode identical with example 1, difference is to use 5.77g C6FA, 0.15g IS, 0.07g AB1 and 14g solvent Y, and uses 0.08g methacrylic acid 2-hydroxyl ethyl ester [CH
2=C (CH
3) COOCH
2CH
2OH] (hereinafter being called 2HEMA) replacement 0.09gCM.To this test panel, estimate its initial oil repellent and refuse oily weather resistance.It the results are shown in table 1.
[example 3]
Obtain test panel in the mode identical with example 2, difference is to use 5.92g methacrylic acid perfluoro hexyl ethyl ester (hereinafter being called C6FMA) to replace 5.7g C6FA.To this test panel, estimate its initial oil repellent and refuse oily weather resistance.It the results are shown in table 1.
[example 4]
In the glass flask of 50mL, add 5.9g vinylformic acid perfluoro alkyl ethyl [F (CF
2)
nCH
2CH
2OCOCH=CH
2] (the mixture of n=6～n=16; N=8 or the bigger 80 quality % or more that account for; The mean value of n is 8, hereinafter is called CmFA), 0.09g IS, 0.05g 2HEMA, 0.29g ethyl propenoate [CH
2=CHCOOCH
2C
5] (hereinafter being called EA), 0.12g 2,2 '-azo two (2, the 4-methyl pentane nitrile) (hereinafter being called AB2) and 13.6g solvent Y.
With the gas of nitrogen replacement flask interior, sealing then.Flask was kept 15 hours in 60 ℃ hot water bath, stir its inside simultaneously, obtain comprising the clear solution of multipolymer.Then, adopt with example 1 in identical mode obtain test panel.To this test panel, estimate its initial oil repellent and refuse oily weather resistance.It the results are shown in table 1.
[example 5]
Obtain test panel in the mode identical with example 4, difference is to use 5.6g CmFA, 0.09g IS, 0.05g 2HEMA and 13.6g solvent Y, and uses 0.12g cyclohexyl acrylate (hereinafter being called CHA) to replace 0.29g EA.To this test panel, estimate its initial oil repellent and refuse oily weather resistance.It the results are shown in table 1.
[example 6]
Obtain test panel in the mode identical with example 4, difference is to use 5.6g CmFA, 0.09g IS, 0.05g 2HEMA and 0.29g EA, and uses 0.09g AB1 to replace AB2, uses 13.6g CF
3(CF
2)
4CHF
2Replace solvent Y, use 70 ℃ hot water bath to replace 60 ℃ hot water bath.To this test panel, estimate its initial oil repellent and refuse oily weather resistance.It the results are shown in table 1.
[example 7]
Add 99.75g methyl ethyl ketone, 0.25g Stilbene base coloured material, stirring then becomes homogeneous phase solution, obtains solution D.In the 99.5g trifluoroethanol, add 0.5g oxa-anthryl coloured material, stirring then becomes homogeneous phase solution, obtains solution E.
In the copolymer solution (2 quality %) of 100g example 1, add 10g solution D and 20g solution E, reach homogeneous state by stirring then.Use this solution, obtain test panel in the mode identical with example 4.Compare with example 1, the oil repellent membrane portions of this test panel has peach painted, and when with the light beam irradiates of 365nm, this oil repellent membrane portions can be luminous, thereby makes the oil repellent film can be by visual confirmation.
[example 8]
In the glass flask of 50mL, add 6g C6FA, 0.09g AB1 and 14g solvent Y.With the gas of nitrogen replacement flask interior, sealing then.Flask was kept 20 hours in 60 ℃ hot water bath, stir its inside simultaneously, obtain comprising the clear solution of multipolymer.Then, adopt with example 1 in identical mode obtain test panel.To this test panel, estimate its initial oil repellent and refuse oily weather resistance.It the results are shown in table 1.
[example 9]
In the glass flask of 50mL, add 6g CmFA, 0.09g AB2 and 14g solvent Y.With the gas of nitrogen replacement flask interior, sealing then.Flask was kept 20 hours in 60 ℃ hot water bath, stir its inside simultaneously, obtain comprising the clear solution of multipolymer.Then, adopt with example 1 in identical mode obtain test panel.To this test panel, estimate its initial oil repellent and refuse oily weather resistance.It the results are shown in table 1.
[example 10]
In withstand voltage glass reaction still, add 100g CF
2=CFOCF
2CF
2CF=CF
2(hereinafter being called CY), 0.5g CH
3OH is as chain-transfer agent and 0.7g ((CH
3)
2CHOC (O) O)
2) as polymerization starter, sealing then.This reactor inside was kept 22 hours at 40 ℃, carry out polyreaction, obtain polymkeric substance thus.The limiting viscosity of formed polymkeric substance in 30 ℃ perfluor (2-butyl tetrahydrofuran) is 2dL/g.
With formed polymkeric substance in hot air circulate type stove under atmospheric atmosphere 300 ℃ of thermal treatments 1 hour, then under 110 ℃ in ultrapure water the dipping 1 week, 100 ℃ of following vacuum-dryings 24 hours, obtain polymkeric substance G then.
As with IR spectrum analytical results to polymkeric substance G, confirmed a peak that belongs to carboxyl, in addition, polymkeric substance G has 108 ℃ glass transition temperature, 25 ℃ hard, transparent, glassy, transmittance is 95% or bigger.Further, 10% pyrolysis temperature of polymkeric substance G is 465 ℃.Obtain solution by 2g polymkeric substance G is dissolved in the 99g PFO, adopt with example 1 in identical mode obtain test panel.To this test panel, estimate its initial oil repellent and refuse oily weather resistance.It the results are shown in table 1.
[table 1]
| Polymerized unit (quality %) | Example 1 | Example 2 | Example 3 | Example 4 | Example 5 | Example 6 | Example 7 | Example 8 | Example 9 | Example 10 | |
| a1 | C6FA | 96.4 | 96.3 | - | - | - | - | 96.4 | 100 | - | - |
| C6FMA | - | - | 96.4 | - | - | - | - | - | - | - | |
| CmFA | - | - | - | 93.2 | 95.6 | 93.2 | - | - | 100 | - | |
| a2 | IS | 2.0 | 2.5 | 2.4 | 1.4 | 1.5 | 1.4 | 2.0 | - | - | - |
| a3 | CM | 1.5 | - | - | - | - | - | 1.5 | - | - | - |
| 2HEMA | - | 1.2 | 1.1 | 0.8 | 0.9 | 0.8 | - | - | - | - | |
| a4 | EA | - | - | - | 4.6 | - | - | - | - | - | - |
| CHA | - | - | - | - | 2.0 | 4.6 | - | - | - | - | |
| CY | - | - | - | - | - | - | - | - | - | 100 | |
| Initial oil repellent (degree) | 77.1 | 72.2 | 71.0 | 74.8 | 76.7 | 75.5 | 76.0 | 71.7 | 71.7 | 53.0 | |
| Refuse oily weather resistance (degree) | 73.8 | 70.5 | 67.7 | 73.9 | 75.8 | 67.6 | 74.3 | 42.8 | 42.8 | 47.2 | |
Industrial applicibility
Oil repellent composition of the present invention can be as the application of oil sealing agent.In addition, oil repellent composition of the present invention not only has good oil repellent, and has good water repellency, makes it can be used in various protective membranes, for example antifouling film etc.It can be as the protective membrane of the water repellency of fiber and oil repellent film, the antifouling film of inkjet head, semi-conductive waterproof and moisture barrier films, semiconductor wafer etc.
Although the present invention at length is described with reference to its embodiment, can carry out various changes and modifications to it in the case of without departing from the spirit and scope will be conspicuous for those skilled in the art.
The application is that its content is included in this as a reference based on the Japanese patent application No. 2005-185577 of Japanese patent application No. 2005-097043 that submitted on March 30th, 2005 and submission on June 24th, 2005.
Claims (10)
1. oil repellent composition comprises:
Multipolymer (A), its have (methyl) acrylate (a1) that is derived from polyfluorinated alkyl polymerized unit, be derived from the polymerized unit of (methyl) acrylate (a2) that contains the blocked isocyanate base and be derived from (methyl) acrylate (a3-1) of hydroxyl or the polymerized unit of (methyl) vinylformic acid (a3-2); With
Solvent.
2. according to the oil repellent composition of claim 1, wherein said multipolymer (A) also has the polymerized unit that is derived from (methyl) acrylate (a4) that contains alkyl.
3. according to the oil repellent composition of claim 1 or 2, the ratio of polymerized unit in multipolymer (A) that wherein is derived from (methyl) acrylate (a1) is 70～98 quality % of total polymerization unit (100 quality %).
4. according to claim 1,2 or 3 oil repellent composition, wherein said oil repellent composition also comprises at least a coloured material.
5. according to the oil repellent composition of claim 4, wherein said coloured material is the fluorescent color material.
6. oil repellent film, comprise multipolymer (A), described multipolymer (A) have (methyl) acrylate (a1) that is derived from polyfluorinated alkyl polymerized unit, be derived from the polymerized unit of (methyl) acrylate (a2) that contains the blocked isocyanate base and be derived from (methyl) acrylate (a3-1) of hydroxyl or the polymerized unit of (methyl) vinylformic acid (a3-2).
7. according to the oil repellent film of claim 6, wherein said multipolymer (A) also has the polymerized unit that is derived from (methyl) acrylate (a4) that contains alkyl.
8. according to the oil repellent film of claim 6 or 7, the ratio of polymerized unit in multipolymer (A) that wherein is derived from (methyl) acrylate (a1) is 70～98 quality % of total polymerization unit (100 quality %).
9. according to claim 6,7 or 8 oil repellent film, wherein said oil repellent composition also comprises at least a coloured material.
10. according to the oil repellent film of claim 9, wherein said coloured material is the fluorescent color material.
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2005097043 | 2005-03-30 | ||
| JP097043/2005 | 2005-03-30 | ||
| JP185577/2005 | 2005-06-24 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN101151319A true CN101151319A (en) | 2008-03-26 |
Family
ID=39251247
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CNA2006800106851A Pending CN101151319A (en) | 2005-03-30 | 2006-03-22 | Oil-repellent composition and oil-repellent film |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN101151319A (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102666773A (en) * | 2009-12-25 | 2012-09-12 | 旭硝子株式会社 | Water-and-oil repellant composition, process for producing same, and method for treating article |
| CN104271690A (en) * | 2012-05-11 | 2015-01-07 | 大金工业株式会社 | Coating composition for water-proofing and moisture-proofing |
| CN104870499A (en) * | 2012-12-14 | 2015-08-26 | 昭和电工株式会社 | Copolymer and photosensitive resin composition and resin film containing said copolymer |
-
2006
- 2006-03-22 CN CNA2006800106851A patent/CN101151319A/en active Pending
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102666773A (en) * | 2009-12-25 | 2012-09-12 | 旭硝子株式会社 | Water-and-oil repellant composition, process for producing same, and method for treating article |
| CN104271690A (en) * | 2012-05-11 | 2015-01-07 | 大金工业株式会社 | Coating composition for water-proofing and moisture-proofing |
| CN104271690B (en) * | 2012-05-11 | 2016-10-19 | 大金工业株式会社 | Coating composition waterproof, damp proof |
| TWI572683B (en) * | 2012-05-11 | 2017-03-01 | Daikin Ind Ltd | Waterproof ‧ Moisture resistant coating composition |
| CN104870499A (en) * | 2012-12-14 | 2015-08-26 | 昭和电工株式会社 | Copolymer and photosensitive resin composition and resin film containing said copolymer |
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